Method of forming a metal oxide film

ABSTRACT

A method of forming a dielectric film composed of metal oxide under an atmosphere of activated vapor containing oxygen. In the method of forming the dielectric film, a metal oxide film is formed on a semiconductor substrate using a metal organic precursor and O 2  gas while the semiconductor substrate is exposed under activated vapor atmosphere containing oxygen, and then, the metal oxide film is annealed while the semiconductor substrate is exposed under activated vapor containing oxygen. The annealing may take place in situ with the formation of the metal oxide film, at the same or substantially the same temperature as the metal oxide forming, and/or at at least one of a different pressure, oxygen concentration, or oxygen flow rate as the metal oxide forming.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This is a divisional application of U.S. application Ser. No.10/131,473 filed on Apr. 25, 2002, the entire contents of which arehereby incorporated by reference for which priority is claimed under 35U.S.C. § 120; and this application claims priority of Application No.01-55468 filed in the Republic of Korea on Sep. 10, 2001 under 35 U.S.C.§ 119.

FIELD OF THE INVENTION

[0002] The present invention relates to a method of forming a metaloxide layer, and more particularly, to a method of forming a metal oxidelayer, which can be used in a semiconductor device.

DESCRIPTION OF THE RELATED ART

[0003] A tantalum pentoxide (Ta₂O₅) film has high dielectric constantand therefore, extensive practical use as a dielectric film in acapacitor for a new generation high-density DRAM of 1 giga bit or more.In order to put a tantalum pentoxide film into practical use, itsleakage current characteristics should also be good.

[0004] Generally, a tantalum pentoxide film is formed by thermalchemical vapor deposition (CVD). During the thermal CVD, a metal organicprecursor, such as Ta(OC₂H₅)₅ as a metal source, and O₂ gas are used.However, impurities such as carbon and moisture may be included in thetantalum pentoxide film, which may provide a path for leakage current.Further, once the tantalum pentoxide film is formed, it is amorphous; asa result its film quality may be poor, and it may be difficult tocombine with oxygen. Accordingly, electric current flowing through sucha film is prone to leak, and oxygen deficiency may occur.

[0005] In a conventional method, a low-temperature oxidation annealingprocess is performed after a tantalum pentoxide film is formed in orderto reduce a leakage current in the tantalum pentoxide film and improvethe characteristics thereof as a dielectric film. Thereafter, thetantalum pentoxide film is heated at high temperature under an oxygenatmosphere to crystallize the tantalum pentoxide film and removeimpurities in the tantalum pentoxide film.

[0006] According to the conventional method, a deposition process offorming a tantalum pentoxide (Ta₂O₅) film and a low-temperatureoxidation annealing process for supplementing oxygen deficiency areindividually accomplished at different process temperatures. For thisreason, two chambers are needed to perform these two processes. If thesetwo processes are to be accomplished in the same chamber, it would takea long time to stabilize the temperature of the chamber. Therefore, timeis wasted and throughput decreased.

[0007] These problems of the conventional method can occur during theformation of a metal oxide film to be used as a dielectric film in asemiconductor device, as well as in a process of forming a tantalumpentoxide (Ta₂O₅) film.

SUMMARY OF THE INVENTION

[0008] At least one embodiment of the present invention provides amethod of forming a tantalum pentoxide film, which reduces the timerequired for an annealing process performed to cure an oxygen deficiencyoccurring after the formation of the tantalum pentoxide film, therebyenhancing the film characteristics and throughput.

[0009] At least one embodiment of the present invention provides amethod of forming a dielectric film, for a semiconductor device, using ametal oxide, which enhances the film characteristics and throughput.

[0010] At least one embodiment of the present invention provides amethod of forming an amorphous tantalum pentoxide or dielectric filmwhere annealing is performed in situ with the formation of the amorphoustantalum pentoxide or metal oxide film.

[0011] At least one embodiment of the present invention provides amethod of forming an amorphous tantalum pentoxide or dielectric filmwhere annealing is performed at the same or substantially the sametemperature as the temperature used during the formation of theamorphous tantalum pentoxide or metal oxide film.

[0012] In at least one embodiment of the present invention the activatedvapor may be one of O₃ gas, UV—O₃, O₂ plasma, O₃ plasma, and N₂O plasma.In at least one embodiment of the present invention, the Ta source maybe one of Ta(OC₂H₅)₅ and Ta(OC₂H₅)₄OCHCH₂N(CH₃)₂.

[0013] In at least one embodiment of the present invention, theconcentration of the activated vapor during annealing is the same as orlarger than the concentration of the activated vapor used during thedeposition of the amorphous tantalum pentoxide film. In at least oneembodiment of the present invention, O₂ gas as well as the activatedvapor may be supplied to the substrate during the annealing. In at leastone embodiment of the present invention, the annealing is performed at atemperature of 380-520° C. In at least one embodiment of the presentinvention, the formation of the amorphous tantalum pentoxide film andthe annealing may be performed at the same or substantially the sametemperature.

[0014] In at least one embodiment of the present invention, theannealing may be performed at a higher pressure than the pressure whenthe amorphous tantalum pentoxide film was formed. For example, theamorphous tantalum pentoxide film may be formed at a pressure of 0.1-10Torr, and the annealing may be performed at a pressure of 0.1-50 Torr.

[0015] In at least one embodiment of the present invention, forming theamorphous tantalum pentoxide film and performing the annealing can berepeated several times until a tantalum pentoxide film is formed to adesired thickness. In at least one embodiment of the present invention,the amorphous tantalum pentoxide film can be crystallized afterannealing.

[0016] At least one other embodiment of the present invention isdirected to a method of forming a tantalum pentoxide film comprising:forming an amorphous pentoxide film on a substrate in a chamber in whichan activated vapor atmosphere containing oxygen is maintained, using aTa source and O₂ gas; and annealing the amorphous tantalum pentoxidefilm in-situ with the formation of the amorphous pentoxide film in anoxygen atmosphere at a lower temperature than the crystallization oftantalum pentoxide.

[0017] In yet another embodiment, the chamber can be purged while it isevacuated, between forming the amorphous tantalum pentoxide film and theannealing.

[0018] At least one other embodiment of the present invention isdirected to a method of forming a dielectric film comprising: forming ametal oxide film on a substrate while the substrate is exposed to afirst activated vapor containing oxygen, using a metal organicprecursor; and annealing the metal oxide film in-situ with the formationof the metal oxide film while the substrate is exposed to a secondactivated vapor containing oxygen.

[0019] In at least one embodiment of the present invention, the metaloxide film may be one of a tantalum pentoxide film, an aluminum oxidefilm, a (Ba,Sr)TiO₃ (BST) film, and a PbZrTiO₃ (PZT) film.

[0020] In at least one embodiment of the present invention, during theformation of the metal oxide film, the metal organic precursor, theactivated vapor, and O₂ gas may be supplied to the substrate. Further,in at least one embodiment of the present invention, during theannealing, the activated vapor and O₂ gas may be supplied to thesubstrate.

[0021] In at least one embodiment of the present invention, theformation of the metal oxide film and the annealing may be performed atthe same or substantially the same temperature. Also, in at least oneembodiment of the present invention, the formation of the metal oxidefilm and the annealing may be performed in the same chamber whilemaintaining the vacuum state of the chamber.

[0022] At least one other embodiment of the present invention isdirected to a method of forming a dielectric film comprising: forming ametal oxide film on a substrate by supplying at least an metal organicprecursor and an activated vapor; and annealing the metal oxide film atsubstantially the same temperature as the a temperature used to form themetal oxide film.

[0023] At least one other embodiment of the present invention isdirected to a method of forming a dielectric film comprising: forming ametal oxide film on a substrate by supplying at least an metal organicprecursor and an activated vapor, under a first pressure, a first vaporconcentration, and a first vapor flow rate; and annealing the metaloxide film under a second pressure, a second vapor concentration, and asecond vapor flow rate, wherein at least one of the second pressure,second vapor concentration, and second vapor flow rate is different fromthe first pressure, the first vapor concentration, and the first vaporflow rate used to form the metal oxide film.

[0024] According to one or more embodiments of the present invention, inorder to form a dielectric film composed of a metal oxide, little or noadditional time is required to stabilize the temperature of the chamberduring the deposition of an amorphous dielectric film and a subsequentannealing, thereby raising throughput. Also, during the deposition ofthe amorphous dielectric film and the subsequent annealing, it ispossible to improve deposition characteristics such as step coverage anddeposition rate and electric characteristics such as leakage currentcharacteristics by appropriately controlling the concentration ofactivated vapor containing oxygen and the flow rate and pressure of O₂gas.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The above objectives and advantages of the present invention willbecome more apparent by describing in detail a preferred embodimentthereof with reference to the attached drawings in which:

[0026]FIGS. 1 through 3 are cross-sectional views for explaining amethod of forming a dielectric film according to at least one embodimentof the present invention;

[0027]FIG. 4 is a graph showing variations in temperature according toprocessing time in a method of forming a tantalum pentoxide filmaccording to at least one embodiment of the present invention;

[0028]FIG. 5 is a graph showing variations in pressure according toprocessing time in a method of forming a tantalum pentoxide filmaccording to at least one embodiment of the present invention;

[0029]FIG. 6 is a graph showing variations in the concentration of O₃according to processing time in a method of forming a tantalum pentoxidefilm according to at least one embodiment of the present invention; and

[0030]FIG. 7 is a graph showing variations in the thickness of atantalum pentoxide film according to deposition time in a method offorming the tantalum pentoxide film according to at least one embodimentof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0031]FIGS. 1 through 3 are cross-sectional views for explaining thesequence of a process of forming a dielectric film according to at leastone embodiment of the present invention.

[0032] Referring to FIG. 1, a lower electrode 20 is formed on asemiconductor substrate 10, and then an amorphous dielectric film 30 isformed thereon. The amorphous dielectric film 30 may be formed bychemical vapor deposition (CVD) using a metal organic precursor as ametal source and O₂ gas. The amorphous dielectric film 30 may be formedof a metal oxide film such as a tantalum pentoxide film, an aluminumoxide film, a (Ba,Sr)TiO₃ (BST) film, a PbZrTiO₃ (PZT) film. The CVD maybe performed in a reaction chamber included in single-wafer typeadopting a resistance heater, and activated vapor containing oxygen, aswell as a metal organic precursor and O₂ gas, is supplied to thereaction chamber during the CVD. For the activated vapor containingoxygen, O₃, UV—O₃, O₂ plasma, O₃ plasma, and/or N₂O plasma may be used.

[0033] Further, Ta(OC₂H₅)₅ or Ta(OC₂H₅)₄OCHCH₂N(CH₃)₂ can be used as aTa source when the amorphous dielectric film 30 is formed of anamorphous tantalum oxide film. The amorphous tantalum oxide film isobtained by maintaining the temperature of the reaction chamber to beabout 380-520° C. (preferably, about 440-480° C.), the pressure to beabout 0.1-10 Torr (preferably, about 1-3 Torr) and supplying Ta(OC₂H₅)₅at a rate of about 30-40 mg/min, O₂ gas at a rate of about 50-1000 sccm(preferably, 50-200 sccm) and O₃ gas at a rate of 10-150 g/m³(preferably, 10-30 g/m³). As a result, the amorphous tantalum oxide filmis formed as the amorphous dielectric film 30 on the lower electrode 20.

[0034] If the amorphous dielectric film 30 is formed of an aluminumoxide film, Al(CH₃)₃ can be used as an aluminum source. Further, if theamorphous dielectric film 30 is formed of the BST film, Ba(C₁₁H₁₉O₂)₂,{Sr(C₁₁H₁₉O₂)₂}₃(C₁₁H₂₀O₂) and/or Ti(C₃H₄O)₄ can be supplied as metalsources. When the amorphous dielectric film 30 is formed of the PZTfilm, Pb(C₁₁H₁₉O₂), Zr(C₄H₉O)₄, and/or Ti(C₃H₇O)₄ can be used as metalsources.

[0035] The above metal sources for the metal oxide films are, however,illustrative and are not meant to restrict the present invention. Exceptfor the supply of the exemplified metal sources, the other conditionsrequired in forming the respective metal oxide film may be the same asor different from those required in forming a tantalum oxide film.

[0036] After the amorphous dielectric film 30 is formed, the chamber maybe purged for approximately 10-120 seconds, while maintained in avacuum, to remove all or most of the metal sources that remain in thesemiconductor substrate 10 having the amorphous dielectric film 30. Atthis time, O₂ gas can be supplied to the chamber.

[0037] Referring to FIG. 2, annealing 32 may be performed on theamorphous dielectric film 30 at about 380-520° C., which is lower thanthe crystallization temperature of the dielectric film 30, underactivated vapor containing oxygen. The annealing 32 may be performed inthe above purged chamber in-situ after the amorphous dielectric film 30is formed, while vacuum is still maintained. To perform the annealing 32under an oxygen atmosphere, activated vapor, such as O₃, UV—O₃, O₂plasma, O₃ plasma and/or N₂O plasma, is supplied to the chamber. Duringthe annealing 32, the concentration of the activated vapor should be thesame as or larger than that of the activated vapor supplied to theamorphous dielectric film 30, and the chamber should be maintained at ahigher pressure than the pressure when forming the amorphous dielectricfilm 30.

[0038] When the amorphous pentoxide film is formed as the amorphousdielectric film 30, the semiconductor substrate 10 may be maintained ata temperature of about 380-520° C. (preferably, about 440-480° C.) and apressure of about 0.1-50 Torr (preferably, about 25-35 Torr). Also, O₂gas at a rate of about 50-20000 sccm (preferably, 1000-20000 sccm) andO₃ gas at a pressure of about 10-150 g/m³ (preferably, 130-150 g/m³) maybe supplied to the semiconductor substrate 10. More preferably, duringthe annealing 32, the chamber is kept at the same or substantially thesame temperature as when the amorphous dielectric film 30 is formed.

[0039] As described above, the formation of the amorphous dielectricfilm 30 and the annealing 32 are performed at the same or substantiallythe same temperature; instead, parameters, such as the pressure, theconcentration of activated vapor containing oxygen and the flow rate andpressure of O₂ gas that may be properly controlled. For this reason,additional time is not required to stabilize the temperature of thechamber, thereby increasing the throughput. Further, depositioncharacteristics such as step coverage and deposition rate and electricalcharacteristics such as leakage current characteristics can be enhanced.

[0040] The amorphous dielectric film 30 may be formed to a desiredthickness, e.g., 100 Å, by the method described with reference to FIG.1, and then, the annealing 32 described with reference to FIG. 2 may beperformed on the amorphous dielectric film 30. Additionally, referringto FIGS. 1 and 2, the formation of amorphous dielectric film 30 and theannealing 32 can be repeated more than once to form a dielectric film ata desired thickness. For instance, in order to obtain a dielectric filmof 100 Å thickness, an amorphous dielectric film 30 having a thicknessof 10 Å may be formed, and the annealing 32 is performed thereon. Then,other amorphous dielectric film having a thickness of 10 Å may be formedon the formed amorphous dielectric film 30 and the annealing 32 isperformed thereon. This process is repeated a number of times until adielectric film having the desired thickness of 100 Å is obtained.

[0041] Referring to FIG. 3, a thermal treatment 34 may be applied to theamorphous dielectric film 30, on which the annealing 32 is performed, ata higher temperature than the crystallization temperature of a tantalumpentoxide film, thereby forming a crystallized dielectric film 30 a. Ifthe amorphous dielectric film 30 is formed of an amorphous tantalumpentoxide film, the amorphous dielectric film 30 is heated at about720-750° C. to form the crystallized dielectric film 30 a.

[0042]FIG. 4 is a graph illustrating variations in temperature accordingto processing time when a tantalum pentoxide film is formed according atleast one embodiment of the present invention. Referring to FIG. 4,before forming a tantalum pentoxide film, the temperature in the chamberis raised to a first temperature. At this time, O₂ gas is preferablyfirst supplied to the chamber to reduce the possibility of a rapidchange in the pressure of the chamber. Once the temperature of thechamber has been raised to a desired temperature, e.g., about 460° C., awafer is loaded in the chamber, and the deposition of a tantalumpentoxide film, the purging of the chamber, and annealing using O₃ areperformed, while the temperature of the chamber is maintained constantor substantially constant. Thereafter, the temperature of the chamber islowered and the wafer is removed from the chamber. At this time, O₂ gasmay be supplied to the chamber so that the possibility of a rapid changein the pressure in the chamber can be reduced.

[0043]FIG. 5 is a graph showing variations in the pressure of a chamberaccording to processing time when a tantalum pentoxide film is formedaccording to at least one embodiment of the present invention.

[0044]FIG. 6 is a graph showing a variation in the concentration of O₃used as activated vapor containing oxygen when a tantalum pentoxide filmis formed according to at least one embodiment of the present invention.

[0045] It is noted that the principles illustrated by FIGS. 4-6 withrespect to tantalum pentoxide films may also be applied the other typesof films mentioned herein, as would be evident to one ordinary skill inthe art, when presented with the discussion above regarding tantalumpentoxide films.

[0046] In a method of forming a tantalum pentoxide film according to atleast one embodiment of the present invention, it is possible to form atantalum pentoxide film having a desired thickness by repeatedlydepositing a tantalum pentoxide film, purging of a chamber, andannealing a desired number of times.

[0047]FIG. 7 is a graph showing variations in the thickness of atantalum pentoxide film according to deposition time in a method offorming the tantalum pentoxide film according to at least one embodimentof the present invention. From FIG. 7, it is noted that the tantalumpentoxide film can be stably deposited by supplying all of a Ta source,O₂ gas, and activated O₃ gas to a chamber once.

[0048] According to at least one embodiment of the present invention, adielectric film composed of a metal oxide may be obtained by supplying ametal source, O₂ gas, and activated vapor containing oxygen in a chamberall at once to form a metal oxide film, and then annealing the amorphousmetal oxide film in the same chamber without a change in temperature,i.e., in situ, under activated vapor atmosphere containing oxygen tosupplement oxygen deficiency in the amorphous metal oxide film. For thisreason, no additional time is required to stabilize the temperature ofthe chamber during the deposition of an amorphous dielectric film and asubsequent annealing, thereby raising throughput. Also, during thedeposition of the amorphous dielectric film and the subsequentannealing, it is possible to improve deposition characteristics such asstep coverage and deposition rate and electric characteristics such asleakage current characteristics by appropriately controlling theconcentration of activated vapor containing oxygen and the flow rate andpressure of O₂ gas.

[0049] While the present invention has been particularly shown anddescribed with reference to the preferred embodiments thereof, thepresent invention is not restricted to the above embodiments. It isnoted that many of the principles described above with respect totantalum pentoxide films may also be applied the other types of filmsmentioned herein, as would be evident to one ordinary skill in the art,when presented with the discussion above regarding tantalum pentoxidefilms.

What is claimed is:
 1. A method of forming a tantalum pentoxide filmcomprising: forming an amorphous tantalum pentoxide film on a substratein a chamber in which an activated vapor atmosphere containing oxygen ismaintained, using a Ta source and O₂ gas at a deposition temperature ofat least 380° C.; and annealing the amorphous tantalum pentoxide film inthe chamber in-situ with the formation of the amorphous pentoxide filmin an oxygen atmosphere at an annealing temperature that is equal to orgreater than the deposition temperature and below a crystallizationtemperature of tantalum pentoxide.
 2. The method of claim 1, wherein theactivated vapor atmosphere containing oxygen includes at least one ofO₃, UV—O₃, O₂ plasma, O₃ plasma and N₂O plasma.
 3. The method of claim1, wherein the Ta source includes at least one of Ta(OC₂H₅)₅ andTa(OC₂H₅)₄OCHCH₂N(CH₃)₂.
 4. The method of claim 1, wherein during theannealing, the oxygen atmosphere includes at least one of O₃, UV—O₃, O₂plasma, O₃ plasma, and N₂O plasma.
 5. The method of claim 4, wherein aconcentration of the oxygen atmosphere during the annealing is the sameor larger than a concentration of the activated vapor atmospherecontaining oxygen used when the amorphous tantalum pentoxide film isformed.
 6. The method of claim 4, wherein during the annealing, O₂ gasand the oxygen atmosphere are supplied to the chamber.
 7. The method ofclaim 4, wherein the annealing temperature is 380-520° C.
 8. The methodof claim 1, wherein the deposition temperature during the formation ofthe amorphous tantalum pentoxide film and the annealing temperature aresubstantially the same temperature.
 9. The method of claim 1, whereinthe annealing is performed while maintaining a vacuum state of thechamber after the amorphous tantalum pentoxide film is formed.
 10. Themethod of claim 1, wherein a pressure during the annealing is higherthan a pressure during the forming of the amorphous tantalum pentoxidefilm.
 11. The method of claim 1, wherein the formation of the amorphoustantalum pentoxide film is performed at a pressure of 0.1-10 Torr. 12.The method of claim 1, wherein the annealing is performed at a pressureof 0.1-50 Torr.
 13. The method of claim 1 further comprising purging thechamber, after forming the amorphous tantalum pentoxide film and beforethe annealing.
 14. The method of claim 13, wherein during the purging ofthe chamber, O₂ gas is supplied to the chamber.
 15. A method of forminga dielectric film comprising: forming a metal oxide film on a substratewhile the substrate is exposed to a first activated vapor containingoxygen, using a metal organic precursor; and annealing the metal oxidefilm in-situ with the formation of the metal oxide film while thesubstrate is exposed to a second activated vapor containing oxygen. 16.The method of claim of 15, wherein the metal oxide film comprises one ofa tantalum pentoxide film, an aluminum oxide film, a (Ba,Sr)TiO₃ (BST)film, and a PbZrTiO₃ (PZT) film.
 17. The method of claim 15, wherein atleast one of the first and second activated vapors containing oxygenincludes at least one of O₃, UV—O₃, O₂ plasma, O₃ plasma, and N₂Oplasma.
 18. The method of claim 15, wherein during the formation of themetal oxide film, the metal organic precursor, the first activated vaporcontaining oxygen, and O₂ gas are supplied to the substrate.
 19. Themethod of claim 15, wherein during the annealing, the second activatedvapor containing oxygen and O₂ gas are supplied to the substrate. 20.The method of claim 15, wherein the annealing is performed at atemperature of 380-520° C.
 21. The method of claim 15, wherein theformation of the metal oxide film and the annealing are performed atsubstantially the same temperature.
 22. The method of claim 15, whereinthe formation of the metal oxide film and the annealing are performed inthe same chamber while maintaining the vacuum state of the chamber. 23.The method of claim 15, wherein the annealing is performed at a higherpressure than the pressure at which the metal oxide film is formed. 24.The method of claim 15, wherein during the annealing, the concentrationof the activated vapor is greater than the concentration of theactivated vapor used when the metal oxide film was formed.
 25. A methodof forming a dielectric film comprising: forming a metal oxide film on asubstrate by supplying at least an metal organic precursor and anactivated vapor at a formation temperature; and annealing the metaloxide film at substantially the same temperature as the formationtemperature used when forming the metal oxide film.
 26. A method offorming a dielectric film comprising: forming a metal oxide film on asubstrate by supplying at least an metal organic precursor and anactivated vapor, under a first pressure, a first vapor concentration,and a first vapor flow rate; and annealing the metal oxide film under asecond pressure, a second vapor concentration, and a second vapor flowrate, wherein at least one of the second pressure, second vaporconcentration, and second vapor flow rate is different from the firstpressure, the first vapor concentration, and the first vapor flow rateused to form the metal oxide film.